Fibrous crosslinked (aminoalkyl)amino-chlorodeoxycellulose and method of preparation

ABSTRACT

THE PREPARATION OF CELLULOSIC YARNS AND FABRICS HAVING 0.67%-11% OF THE CELLULOSIC HYDROXYL GROUPS REPLACED BY CHLORINE ATOMS, AND A FURTHER 0.33%-7% OF THE HYDROXYL GROUPS REPLACED BY (AMINOALKYL) AMINO GROUPS, IN ADDITION TO APPRECIABLE CELLULOSE CROSSLINKING, LEADS TO TEXTILES OF INCREASED WRINKLE RESISTANCE IN THE WET STATE, ENHANCED AFFINITY FOR ACID DYES, AND INCREASED RESISTANCE TO CELLULOSE SOLVENTS. THE CELLULOSIC TEXTILE IS FIRST CONVERTED TO CHLORODEOXYCELLULOSE IN TEXTILE FORM, BY REACTION WITH THIONYL CHLORIDE IN DIMETHYLFORMAMIDE AT 20*-30* C., AND IS SUBSEQUENTLY TREATED WITH AN ALIPHATIC POLYAMINE DISSOLVED IN A STRAIGHT-CHAIN ALCOHOL OF 3-6 CARBON ATOMS AT 90*-130*C., TO REPLACE SOME OF THE CHLORINE ATOMS BY (AMINOALKYL)AMINO GROUPS.

United States Patent Ofice 3,698,857 Patented Oct. 17, 1972 FIBROUS CROSSLINKED (AMINOALKYL)AMINO- CHLORODEOXYCELLULOSE AND METHOD OF PREPARATION Tyrone L. Vigo, New Orleans, and Matthew F. Margavio and Clark M. Welch, Metairie, La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Jan. 26, 1971, Ser. No. 109,964

Int. Cl. D06m 13/00, 13/34, 13/54 US. Cl. 8-1162 24 Claims ABSTRACT OF THE DISCLOSURE The preparation of cellulosic yarns and fabrics having 0.67%-ll% of the cellulosic hydroxyl groups replaced by chlorine atoms, and a further 0.33%7% of the hydroxyl groups replaced by (aminoalkyl)amino groups, in addition to appreciable cellulose crosslinking, leads to textiles of increased wrinkle resistance in the wet state, enhanced aflinity for acid dyes, and increased resistance to cellulose solvents. The cellulosic textile is first converted to chlorodeoxycellulose in textile form, by reaction with thionyl chloride in dimethylformamide at 2030 C., and is subsequently treated with an aliphatic polyamine dissolved in a straight-chain alcohol of 3-6 carbon atoms at 90130 C., to replace some of the chlorine atoms by (aminoalkyl)amino groups.

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to a method of introducing (aminoalkyl)amino substituents, together with chloro substituents, into cellulose molecules, as a means of preparing mixed derivatives of cellulose not hitherto described, but having novel properties and uses, particularly as textile materials and intermediates. More specifically, the present invention relates to the conversion of fibrous cellulose in the form of yarn and fabric to chlorodeoxycellulose, and the subsequent replacement of a sizable fraction of the chlorine atoms therein by (aminoalkyl) amino groups, which replacement is accompanied by a very low, controlled degree of cellulose crosslinking utilizing only a small fraction of the total number of (aminoalkyl)amino groups introduced, the resulting crosslinked (aminoalkyl)amino-chlorodeoxyoellulose retaining the fiber form and yarn or fabric structure originally possessed by the untreated cellulose. The types of cellulose to which the processes of this invention are applicable include native, mercerized, and regenerated celluloses derived from cotton and wood pulp. The cellulosic textile products prepared by the processes of this invention possess increased wrinkle resistance, improved dyeing properties, enhanced resistance to attack by solvents for native cellulose, and a capability for undergoing further chemical substitution and crosslinking.

The main object of the present invention is to provide chemically substituted, fibrous celluloses wherein each cellulose molecule contains two kinds of chemical substituents, specifically, chloro and (aminoalkyl)amino substituents, by virtue of replacement of some of the hydroxyl groups of the cellulose by these substituents, the resulting fibrous mixed derivatives of cellulose having utility as textile materials and as intermediates for further substitution, graft polymerization and cellulose crosslinking processes leading to various other textile materials.

A second object of the present invention is to provide a means of introducing a limited and controlled degree of cellulose crosslinking in cellulosic textiles, so as to impart increased wrinkle resistance in the wet state, and increased resistance to attack by cellulose solvents, without causing a loss of tensile strength during the crosslinking step.

A third object of the present invention is to provide a means of rendering cellulosic textiles receptive to acid dyes which lack substantivity for native cellulose.

A fourth object of the present invention is to provide a means of imparting anion-exchange properties, ion-sequestering properties, and other cationic properties to cellulosic textiles, such properties being useful in attaching ionic fungicides, rotproofing agents and other ionic finishing agents to said textiles, and in catalyzing polymerization reactions on the surface of said textiles. Other objects will become apparent in the description of the invention.

The (aminoalkyl)amino chlorodeoxycelluloses of the present invention are formed by the reaction of certain aliphatic polyamines with fibrous chlorodeoxycellulose, the latter being preferably in yarn or fabric form. To prepare the chlorodeoxycellulose yarns and fabrics required for the present processes, the known reaction of thionyl chloride with cellulose may be used. This reaction has hitherto been run only on dispersed cellulose fibers. As the reaction medium, dimethylformamide is advantageous inasmuch as it suppresses cellulose degradation that occurs with other media, as previously shown by Polyakov and Rogovin, Vysokomol. Soedin, 5 [1] 11-17 (1963); Chem. Abs. 59, 6604b 1963). Although these workers recommended reaction temperatures of 60-98 C. in treating cotton linters with thionyl chloride in dimethylformamide, they noted yellowing in the cotton so treated. In the present treatments carried out on cellulosic yarns and fabrics, it is found that such elevated temperatures cause severe tendering as well as yellowing. The preparation of chlorodeoxycellulose yarns and fabrics for use in the processes of the present invention requires the use of lower reaction temperatures, in the range of 20-30 C. Both yellowing and tendering are thereby avoided.

Reaction times of from 30 minutes to 24 hours may be employed in preparing the chlorodeoxycellulose, de pending on the chlorine content desired. Although the reaction with thionyl chloride may be carried out on native cellulose, that has been swollen with water and solvent-exchanged, the reaction is more rapid and complete, and results in higher strength retention in the treated textile, when conducted on cellulose swollen with a mercerizing alkali such as l6%-30% aqueous sodium hydroxide, the aqueous alkali being removed by washing and solvent-exchange prior to treatment of the cellulose with thionyl chloride in dimethylformamide. This washing and solvent-exchange can be done by first washing the cellulose fiber, yarn or fabric with water to remove alkali, then washing with a water-miscible, cellulose-inert solvent such as ethanol to remove water, and finally with an inert aprotic solvent such as benzene to remove the ethanol. Prior to thionyl chloride treatment, the cellulose is not allowed to dry, once it has been swollen, as drying deswells and deactivates it. Reaction of thionyl chloride with the swollen, solvent-exchanged cellulose in dimethylformamide may then be carried out either by adding the thionyl chloride to the suspension of cellulose in dimethyl formamide, or by adding the cellulose to a solution of thionyl chloride in dimethylformamide. The ch10- rodeoxycellulose so produced may be washed with ice water, or with dimethylformamide followed by ice water, to remove excess thionyl chloride, and then with 1%4% aqueous ammonia at room temperature to remove sulfurcontaining byproducts. The yarn may then be washed with water and with acetone, and dried. The concentration of thionyl chloride in the liquid phase of the reaction mixture, during the conversion of cellulose to chlorodeoxycellulose, is preferably kept in the range of 2%20% by weight, lower thionyl chloride concentrations give very slow reaction, while higher concentrations than these tend to induce cellulose degradation.

chlorodeoxycellulose produced in this manner, and suitable for use in carrying out the processes of the present invention, contains 0.6%-7.5% chlorine. The exact chlorine content obtained depends on the reaction time, temperature, thionyl chloride concentration, and whether the cellulose has been mercerized and solventexchanged prior to treatment. In the resulting chlorodeoxycellulose, the numerical ratio of chlorine atoms to anhydroglucose units in the cellulose chains is preferably in the range of 0.03-0.35.

The conversion of cellulose to chlorodeoxycellulose may be represented by the equation cellulose-OH|SOCl cellulose-Cl-l-SO HCl The resulting chlorodeoxycellulose has the capability of reacting with an excess of a simple primary aliphatic amine, RNH at elevated temperatures, as follows:

cellulose-Cl +2RNH cellulose-NHRi-l-RNH HCl Such a reaction brings about the replacement of chlorine atoms in chlorodeoxycellulose by alkylamino groups.

The amines, however, which are found to be suitable for reaction with chlorodeoxycellulose in the processes of the present invention are those aliphatic polyamines having the structure wherein x is an integer having values of from 2 to 6 inclusive, and y is an integer having values of from to l, with y being 0 when x is greater than 2. Under the conditions of the present processes, reaction of the aliphatic polyamine with the chlorodeoxycellulose results in replacement of up to 60% of the chlorine atoms in chlorodeoxycellulose by (aminoalkyl)amino groups having the structure [NH (CH NHCH CH -NH-l, wherein x and y are as defined above. In those instances where dehydrochlorination occurs only to a negligable extent, the ratio of chlorine atoms displaced/nitrogen atoms introduced during the process, as determined by elemental analysis, corresponds closely to the introduction of one such aminoalkylamino group for each chlorine atom displaced. The results obtained indicate that the number of crosslinks of the structure formed in the cellulose is in some instances too small to be detected analytically, but the occurrence of these crosslinks is readily and invariably detectable by the insolubility of the product in cellulose solvents such as 1.0 molar aqueous cupriethylenediamine and by the wrinkle resistance imparted. That the degree of cellulose cross-linking is small is borne out by the considerable swelling that such cellulose solvents induce in the fibers of the product. In order for the product to have the desired properties, the numerical ratio of (aminoa1kyl)amino groups/anhydroglucose units in the product must be in the range of 0.0l-0.2.

The fibrous, water-insoluble (aminoalkyl)amino-ch1orodeoxycelluloses formed as the product of the present processes have the structure wherein at and y are as already defined above, Z repre sents a segment of a crosslinked cellulose chain which segment contains 100 anhydroglucose units, It has value in the range of 3 to 35, b has values in the range of 1 to 20 but does not exceed 0.6 n, the aforesaid crosslinks in Z having the structure the number of these crosslinks being sutficient to impart insolubility of the fibrous product in cellulose solvents such as aqueous 1.0 molar cupriethylenediamine but insufficient to prevent swelling of the fibrous product in said cellulose solvents. As is evident in this structure, the number of chlorine atoms per anhydroglucose units is given by (nb) which has values in the range of 2 to 34.

As already indicated, the introduction of a certain class of (aminoalkyl)amino substituents having the struc ture into chlorodeoxycellulose is necessary to impart the textile properties characteristic of the product of the present invention. If both x and y have values of 0, thus departing from the limits specified above, the products are watersoluble, non-crosslinked hydrazinodeoxycelluloses, which have previously been prepared by Polyakov and Rogovin from the reaction of sodium hydrazide with chlorodeoxycellulose (Vsokomolekul Soedin, T selluylozy 1963 147-9; Chem. Abs. 61, 2045d (1964)). Such hydrazinodeoxycelluloses, by virtue of their water-solubility, are valueless as textiles. Their water-solubility is the result of a complete lack of crosslinking. The water-insolubility and therefore the suitability of the present products as textiles is entirely unexpected, and is apparently due to the appreciable degree of cellulose crosslinking in the present products. The crosslinking also confers wrinkle resistance in the wet state to cellulosic fabrics treated by the present process, thus rendering the fabrics self-smoothing when they are hung on a line and drip-dried.

The process of the present invention, whereby fibrous crosslinked (aminoalkyl)amino-chlorodeoxycelluloses in textile form are obtained, comprises the following steps:

(a) Conversion of fibrous cellulose in textile form to fibrous chlorodeoxycellulose in textile form, the ratio of chlorine atoms to anhydroglucose units in said chlor0deoxycellulose being about from 0.03 to 0.35,

(b) Immersing the chlorodeoxycellulose textile in a so lution of an aliphatic polyamine in a straight-chain aliphatic alcohol having from 3 to 6 carbon atoms, the aliphatic polyamine having the structure wherein x is an integer having values of from 2 to 6 inelusive, and y is an integer having values of from 0 to 1, with y being 0 and x is greater than 2, the concentration of said polyamine in said alcohol being about from 5% to 60% by weight, the temperatures of said solution being about from 90 C. to C., and the duration of said immersion being about from 0.5 hour to 10 hours.

(c) Washing the textile to remove excess polyamine, and

(d) Drying the textile.

Typical examples of aliphatic polyamines suitable for reaction with chlorodeoxycellulose by the above process are the following:

ethylenediamine diethylenetriamine 1,4-butanediamine 1,6-hexanediamine The desired introduction of (aminoalkyl)amino groups is most efiicient and rapid with polyamines of low molecular weight. The process becomes slow and incomplete, and dehydrochlorination of chlorodeoxycellulose becomes important as a side reaction, when amines of higher molecular Weight than those listed here are used. The dehydrochlorination is evidenced by a lower than predicted ratio of nitrogen atoms introduced/chlorine atoms lost during the amine treatment.

formation of such intermediates is far more rapid in solvents of high polarity and high hydrogen-bonding capacity, than in nonpolar, aprotic solvents. The molecular weight of the diluent should be as low as is consistent with these requirements, since high-molecular-weight diluents do not penetrate cellulose readily. Also, the diluent should be chemically inert to the amine and the chlorodeoxycellulose, as well as to the catalytic action of amine hydrochlorides at the reaction temperature used, and should have appreciable water solubility to facilitate removal of the diluent from the product during final washing. Aliphatic alcohols which meet these requirements as diluents include l-propanol, l-butanol, l-pentanol, and l-hexanol.

Reaction temperatures suitable in step (b) of the above process are in the range of 90l30 C., with temperatures of 100-l15 C. being preferred. At low temperatures, the reaction becomes slow and incomplete, while at excessively high temperatures, uncontrolled crosslink-' ing, yellowing and dehydrochlorination of the chlorodeoxycellulose tend to occur. At the prefered temperatures, l-butanol is the diluent of choice, from the standpoint of economy and effectiveness.

As already indicated, the reaction of the aliphatic polyamine with the chlorodeoxycellulose, in step- (b) of the above process, results in replacement of 10%-60% of the chlorine atoms in the chlorodeoxycellulose by (aminoalkyl)amino groups. The ratio of these two substituents in the final product can be adjusted over a wide range by the proper choice of reaction time used in step (b), the reaction commencing when the chlorodeoxycellulose textile is immersed in the heated aliphatic polyamine solution, and ceasing when the textile is removed from this heated solution.

THe washing step (c) in the above process can be carried out with water, or with an inert water-miscible organic solvent followed by water. Suitable organic solvents which facilitate removal of amines occluded in the interior of the treated cellulosic fibers are low molecularweight alcohols such as methanol and ethanol.

The drying step (d) maybe conducted at any convenient temperature that does not cause excessive yellowing or air-oxidation of the (aminoalkyl)amino-chlorodeoxycellulose. Drying temperatures in the range of 20115 C. are preferred.

As already mentioned, the fibrous (aminoalkyl)aminochlorodeoxycellulose obtained as a product of the present invention have utility as an intermediate for further chemical modification, to yield still other textile materials possessing a variety of properties. Examples of subsequent modifications possible, in the substituent groups of the present products, are the reactions of the primary and secondary amino groups therein, with aldehydes such as formaldehyde or glyoxal. Treatment with such aldehydes can lead to further crosslinking of the present products, or to cellulose derivatives having aldimino groups. Likewise the amino groups of the present products are available for reaction with dyes which contain vinylsulfonyl groups, chlorotriazinyl groups or other groups reactive towards active hydrogen compounds. In general, amino groups undergo such reactions more readily and under milder conditions than do hydroxyl groups already present in native cellulose. Removal of chlorine atoms in the present products by hydrolysis or by base-catalyzed de- 6 hydrochlorination is possible, where such removal of chlorine is desirable to permit introduction of still other substituent groups.

In the examples that follow, all parts and percentages are by weight. Wrinkle recovery of treated fabrics was determined with the Monsanto tester.

EXAMPLE 1 Preparation of chlorodeoxycellulose yarn Kjered 12/3 cotton yarn was immersed in 23% aqueous sodium hydroxide for one hour at 25 C., was washed with excess tap water, and was then washed with dis-= tilled water until the washings were neutral to phenol= phthalein indicator. The yarn was afterwards immersed in aqueous ethanol for 24 hours. The yarn was next rinsed several times with benzene, and was soaked in benzene for 24 hours. The yarn was then squeezed to free it of excess benzene, and was immersed in 32 times its own weight of dimethylformamide. While the yarn was immersed in the dimethylformamide, thionyl chloride was added dropwise to the latter, at such a rate as to keep the temperature of the mixture below 30 C., the addition being continued until 8.0 parts by weight of thionyl ch10 ride had been added for each part by weight of yarn. This addition required approximately one hour. The mix-= ture was then shaken in a stoppered container for 4 hours at 25 C. The yarn was then removed from the liquid, was washed with ice water until the washings were only weakly acidic, as indicated by a pH of 4 or greater, and was then washed with water at room temperature. The yarn subsequently was immersed in 3% aqueous ammonium hydroxide for one hour, was washed with water and then with acetone, and was air-dried to yield fibrous chlorodeoxycellulose yarn having a chlorine content of 5.0% (dry basis), an ash content of 0.5% and a moisture content of 8.6%. Fibers of the treated yarn were soluble in 1.0 molar aqueous cupriethylenediamine, show ing the chlorodeoxycellulose was not crosslinked.

The breaking strength of the chlorodeoxycellulose yarn was 5.0 pounds, as compared to 5.4-5.9 pounds for the original untreated yarn. The elongation-at-break was 43.2% for treated yarn as compared to 12.8% prior to treatment. Tenacity of treated yarn was 9.1 g./tex as compared to 17.7 g./tex for untreated yarn. Energy-torupture was 5.6 in.-lbs. for treated yarn, as compared to 2.3 in.-lbs. for untreated yarn. The chlorodeoxycellulose yarn was only faintly colored by water solutions of acid dyes such as Kiton Fast Red 3 GLL (a mixture of Cl. Acid Red 1 and Cl. Acid Red 37), indicating a lack of affinity for such dyes. Similarly, the cotton yarn from which the chlorodeoxycellulose yarn had been prepared was undyed by Kiton Fast Red 3 GLL.

EXAMPLE 2 Reaction of chlorodeoxycellulose yarn with ethylenediamine A sample of the chlorodeoxycellulose yarn prepared by the procedure of Example 1 was immersed in 25 times its own weight of a 10% solution of ethylenediamine in 1- butanol, for 2 hours at C. The yarn was subsequently washed for 10 minutes in 95% aqueous ethanol, then for 20 minutes inalkaline tap water, and was air-dried over night to yield a (2-aminoethyl)amino-chlorodeoxycellulose yarn having on a dry basis a nitrogen content of 0.7%, and a chlorine content of 4.1%. The ash content was 0.7% and moisture content was 8.8%. The elemental analysis indicated 2.0 atoms of nitrogen were introduced for each chlorine atom lost during amine treatment, as required by theory.

Fibers of the product were insoluble in 1.0 molar aque= ous cupriethylenediamine, indicating crosslinking had occurred in the yarn. However, the degree of cross linking was low, as indicated by swelling and ballooning that occurred in the fibers placed in 1.0 molar cupriethylenediamine, and also by the high breaking strength (4.8 lbs.) retained in the yarn as compared to 5.0 lbs. for chlorodeoxycellulose yarn prior to amine treatment. The elongation-at-break of the treated yarn was 35.1%, the tenacity was 9.4 g./tex and energy-to-rupture was 4.7 in.-lbs., which values are further indicative of the smallness of the degree of crosslinking that occurred.

The (2-aminoethyl)amino-ch10rodeoxycellulose yarn was dyed a deep red shade with a water solution of the acid dye Kiton Fast Red 3 GLL, showing that the presence of (aminoethyl)amino groups in the yarn imparted a high afiinity for acid dyes.

In a similar run in which the ethylenediamine concentration used in treating the chlorodeoxycellulose yarn was 50%, the resulting yarn possessed a nitrogen content of 2.2% and a chlorine content of 2.0%, both values being calculated on a dry basis. The ash content was 0.7% moisture content was 9.8% and sulfur content was 0.1%. After correction is made for the yarn weight gain produced when (2-aminoethyl)amino group displaces a chlorine atom in chloro deoxycellulose, the observed nitrogen and chlorine contents correspond to introduction of 1.93 nitrogen atoms for each chlorine atom lost during amine treatment. This is 96% of the value required by theory. The breaking strength of the treated yarn was 4.9 pounds, elongation-at-break was 30.7%, tenacity was 9.3 g./tex and energy to rupture was 4.5 in.-lbs. Fibers of the treated yarns were insoluble in 1.0 molar cupriethylenediamine indicating crosslinking of the cellulose had occurred during amine treatment.

EXAMPLE 3 Reaction of chlorodeoxycellulose yarn with 1,4-butanediamine chlorodeoxycellulose yarn prepared by the procedure of Example 1 was immersed in 25 times its own Weight of a 50% solution of 1,4-butanediamine in l-butanol, for 2 hours at 105 C. The yarn was subsequently washed for minutes in 95% aqueous ethanol, then for minutes in alkaline tap water, and was air-dried overnight to give a (4-aminobutyl)amino-chlorodeoxycellulose yarn having a nitrogen content of 1.6% and a chlorine content of 3.3%, calculated on a dry basis. The ash content was 0.4% and moisture content was 10.3

Fibers of the treated yarn were insoluble in cellulose solvents such as 1.0 molar cupriethylenediamine, indicating some cellulose crosslinking had occurred. However, the degree of crosslinking was low, as indicated by the swelling that occurred in fibers placed in the cellulose solvent, and also by the high breaking strength (5.0 lbs.) retained in treated yarn, which equalled the breaking strength of chlorodeoxycellulose yarn prior to amine treatment. The elongation-at-break was 32.8%, or moderately lower than for chlorodeoxycellulose yarn, again indicating a low degree of crosslinking had occurred during treatment. Yarn tenacity was 9.5 g./tex, while energy-to-rup-= ture was 5.0 in.-lbs., similar to the values for chlorodeoxycellulose yarn.

The (4-aminobutyl)amino-chlorodeoxycellulose yarn was highly receptive to the acid dye Kiton Fast Red 3 GLL, in which it was dyed a deep blood-red shade.

EXAMPLE 4 Reaction of chlorodeoxycellulose yarn with 1,6-hexanediamine chlorodeoxycellulose yarn prepared by the procedure of Example 1 was immersed in times its own weight of a 50% solution of 1,6-hexanediamine in l-butanol, for 2 hours at 105 C. The yarn was subsequently Washed for 10 minutes in 95 aqueous ethanol, then for 20 minutes in alkaline tap water, and was air-dried overnight to yield a (G-arninohexyl) amino-chlorodeoxycellulose yarn having a nitrogen content of 1.0% and a chlorine content of 3.1%, calculated on a dry basis. These values correspond 8 to the introduction of 1.5 nitrogen atoms for each chlorine atom lost during amine treatment, or 75% of the number theoretically predicted. The ash content was 0.3% and moisture content was 8.2%.

Fibers of the resultant yarn were insoluble in cellulose solvents such as 1.0 molar cupriethylenediamine, indicating cellulose crosslinking had occurred in the yarn during amine treatment. The fibers were swollen by the cupriethylenediamine, indicating the degree of cellulose crosslinking was low. The high breaking strength (5.1 lbs.) and elongation-at-break (33.0%) also indicate only slight crosslinking had occurred. The tenacity of the yarn was 9.8 g./tex and energy-to-rupture was 5.1 in.-lbs.

The (6 aminohexyl)amino-chlorodeoxycellulose was highly receptive to the acid dye Kiton Fast Red 3 GLL, in which it was dyed a blood-red shade.

EXAMPLE 5 Preparation of chlorodeoxycellulose fabric from mercerized cotton Cotton x 80 printcloth which had previously been desized, scoured and bleached was mercerized at con stant dimensions in 23% aqueous sodium hydroxide for 30 minutes at 25 C. The cloth was then washed with tap water, and later with distilled water until the washings were neutral to phenolphthalein indicator. The fabric was subsequently rinsed in several portions of aqueous ethanol, then rinsed in several portions of benzene and was then stored immersed in benzene for 4 days. The cloth was then shaken for 21 hours in 40 times its own weight of a 20% solution of thionyl chloride in dimethyl formamide, at 25 C. Subsequently, the cloth was washed with several portions of dimethylformamide, then with ice water until the pH of the washings was 4 or greater, and then with tap water. The cloth was soaked in 3% aqueous ammonium hydroxide for one hour, was then washed in tap water, and finally was given several rinses with acetone, followed by several rinses with water. The cloth was oven-dried for 10 minutes at 90 C. to give chlorodeoxycellulose fabric having a chlorine content of 2.97%.

The chlorodeoxycellulose fabric so produced had a conditioned wrinkle recovery angle (warp-l-fill) of 212, while the wet wrinkle recovery angle was 223". Fibers of this fabric were readily soluble in 1.0 molar cupriethylenediamine.

EXAMPLE 6 Reaction of chlorodeoxycellulose fabric with ethylenediamine chlorodeoxycellulose fabric prepared as in Example 5 was immersed in a 20% solution of diethylenetriamine, l-butanol at C. for 5 hours, the weight of solution used being 25 times the weight of the fabric. At the end of this period, the fabric was washed for 40 minutes in alkaline tap water at 1825 C., then for 30 minutes in alkaline tap water at 5060 C., and oven-dried at 85 C. for 10 minutes. The resulting (2-arninoethyl)amino-= chlorodeoxycellulose fabric had a nitrogen content of 1.16% and a chlorine content of 1.32%. After correction is made for the fabric weight gain produued when a (2= aminoethyl)amino group replaces a chlorine atom in chlo= rodeoxycellulose fabric, the observed nitrogen and chlo= rine contents correspond to introduction of 1.85 nitrogen atoms for each chlorine atom lost during amine treatment. This is 92% of the value required by theory, for the replacement of chlorine by (2-aminoethyl)amino groups.

The resulting fabric had a conditioned wrinkle recovery angle (warp+fill) of 212, and a wet wrinkle recovery angle of 246, indicating it now possessed a useful level of wrinkle resistance in the wet state. The fabric was dyed a deep red color with the acid dye Kiton Fast Red 3 GLL, indicating a strong affinity of this fabric for such dyes, in contrast to cotton which has no appreciable afiinity for such dyes. Fibers of the treated fabric were insoluble in 1.0 molar aqueous cupriethylenediamine, although they were swollen by this cellulose solvent.

EXAMPLE 7 Reaction of chlorodeoxycellulose fabric with diethylenetriamine Chlorodeoxycellulose fabric prepared as in Example was immersed in a 20% silution of diethylenetriamine, also known as bis(2-aminoethyl)a-mine, in l-butanol at 110 C. for 5 hours, the weight of solution used being 25 times the weight of the fabric. At the end of this period, the fabric was washed for 40 minutes in alkaline EXAMPLE 9 Reaction of aliphatic polyamides with chlorodeoxycellulose fabric prepared from unmercerized cotton Wrinkle recovery Jondi- Solubility Aliphatic tioned, Wet, Percent Percent Dye in polyamine degree degree N 01 affinity cuene b Ethylene diamine 206 191 0.2 0.5 Great... Partial. Diethylenetriamine. 195 212 0.3 0.6 .do None. None 189 190 0.03 0.9 None... Complete.

a Kiton Fast Red 3 GLL, an acid dye. b 1.0 molar aqueous cupriethylenediamine, a cellulose solvent.

tap water at 18-25 C., then for 30 minutes in alkaline tap water at 50-60 C., and oven-dried at 85 C. for 10 minutes. The resulting 2-(2-aminoethylamino) ethylamino-chlorodeoxycellulose fabric had a nitrogen content of 1.35% and a chlorine content of 1.48%. These analyses correspond to the introduction of 2.43 nitrogen atoms for each chlorine atom lost during amine treatment. This is 81% of the theoretical value.

The resulting fabric had a conditioned wrinkle recovery angle (war-p+fill) of 207, and a wet wrinkle recovery angle of 251, indicating a useful level of wrinkle re sistance in the wet state, in contrast to untreated fabric or chlorodeoxycellulose fabric. The amine-treated fabric was dyed a deep red color with the acid dye Kiton Fast Red 3 GLL, indicating the process had imparted to the cloth a strong afiinity for such dyes. Fibers of the treated fabric were insoluble in 1.0 molar aqueous cupriethylenediamine, although they were swollen by this cellulose solvent.

EXAMPLE 8 Preparation of chlorodeoxycellulose fabric from unmercerized cotton Cotton 80 x 80 printcloth which had previously been desized, scoured and bleached was wet thoroughly with water to swell and activate the fibers, and was then rinsed several times in 95% aqueous ethanol. The cloth was given several rinses in benzene, then was kept immersed in benzene overnight and afterwards was rinsed in dimethylformamide. Then the cloth was immersed in forty times its weight of a 20% solution of thionyl chloride in dirnethylformamide, at 25 C. for 4 hours. Subsequently the cloth was rinsed several times in dimethylformamide, and later in ice water. It was then soaked in 3% aqueous ammonia for 16 hours at room temperature, to remove sulfur-containing impurities from the fabric. The cloth was washed in water, rinsed several times in acetone, again rinsed in water, and finally was dried at 110 C./4 min.

The resulting fabric had a nitrogen content of 0.03%, a chlorine content of 0.9%, and a sulfur content of 0.5%. Fibers of the treated fabric were completely soluble in 1.0 molar cupriethylenediamine. The cloth remained completely undyed when immersed in an aqueous solution of Kiton Fast Red 3 GLL and subsequently rinsed. The cloth had a conditioned wrinkle recovery angle (warp+fill) of 189, and a wet wrinkle recovery angle of 190.

The nitrogen and chlorine content of the products show that the samples of chlorodeoxycellulose fabric which were treated with an aliphatic polyamine were converted to (aminoalkyl)amino-chlorodeoxycellulose possessing a greatly enhanced afiinity for acid dyes, and a decreased susceptibility to attack by cellulose solvents. In the case where ethylenediamine was the polyamine used, increased conditioned wrinkle recovery was imparted, and when diethylenetriamine was used, increased wet wrinkle re covery was imparted. These wrinkle recovery effects, together with the decreased solubility in cupriethylenedi= amine, are indicative of cellulose crosslinking in the poly amine-treated fabricso We claim:

1. A process for preparing a fibrous, crosslinked (aminoalkyl)aminochlorodeoxycellulose in textile form, comprising:

(a) impregnating a fibrous cellulose textile with an aqueous 16% to 30% sodium hydroxide solution to obtain a swollen fibre structure,

(b) removing the sodium hydroxide by water-waslring and solvent-exchanging with a water-miscible, cellulose-inert solvent, followed by exchanging with an inert aprotic solvent,

(0) reacting the resulting swollen fibrous cellulose with 2% to 20% thionyl chloride in dimethylformarnide solution, for about from 30 minutes to 24 hours, at a temperature of about from 20 C. to 30 C.,

(d) washing the reacted fibrous cellulose with dimethylformamide, ice water, and an aqueous 1% to 4% ammonia solution at room temperature to remove sulfur-containing byproducts and obtain a fibrous chlorodeoxycellulose in textile form containing about from 0.6% to 7.5% chlorine,

(e) immersing and reacting the immersed chlorode-= oxycellulose textile in a solution of aliphatic polyamine in a straight-chain aliphatic alcohol having from 3 to 6 carbon atoms, the aliphatic polyamine having the structure wherein at is an integer having a value of from 2 to 6 inclusive, and y is an integer having a value of from 0 to 1, with y being 0 when x is greater than 2, the concentration of said polyamine in said alcohol being about from 5% to 6% by weight, the temperature of said solution being from about C. to

11 130 C., and the duration of said immersion being about from 0.5 hour to 10 hours.

(t) washing the thus-reacted textile to remove excess polyamine, and

(g) drying the washed textile.

2. The process of claim 1 wherein the water-miscible, cellulose-inert solvent is ethanol.

3. The process of claim 1 wherein the inert aprotic sol= vent is benzene.

4. The process of claim 1 wherein the aliphatic polyamine is ethylenediamine.

5. The process of claim 1 wherein the aliphatic poly amine is 1,4-butanediamine.

6. The process of claim 1 wherein the aliphatic polyamine is 1,6-hexanediamine.

7. The process of claim 1 wherein the aliphatic polyamine is diethylenetriamine.

8. The process of claim 1 wherein the straight-chain alcohol is l-butanol.

9. A process for preparing a fibrous, crosslinked (aminoalkyl)aminochlorodeoxycellulose in textile form, comprising:

(a) impregnating a fibrous cellulose textile with water to swell the cellulose fibers of the textile,

(b) removing the water by solvent-exchanging with a Water-miscible, cellulose-inert solvent, followed by exchanging with an inert aprotic solvent,

() reacting the resulting swollen fibrous cellulose with 2% to 20% thionyl chloride in dimethylformamide solution, for about from 30 minutes to 24 hours, at a temperature of from about 20 C. to 30 C.,

(d) washing the reacted fibrous cellulose with dimethylformamide, ice water, and an aqueous 1% to 4% ammonia solution at room temperature to remove sulfur-containing byproducts and obtain a fibrous chlorodeoxycellulose in textile form containing about from 0.6% to 7.5% chlorine,

(e) immersing and reacting the immersed chlorodeoxycellulose textile in a solution of aliphatic polyamine in a straight-chain aliphatic alcohol having from 3 to 6 carbon atoms, the aliphatic polyamine having the structure wherein x is an integer having a value of from 2 to 6, inclusive, and y is an integer having a value of from 0 to 1, with y being 0 when x is greater than 2, the concentration of said polyamine is said alc0= hol being about from to 60% by weight, the temperature of said solution being about from 90 C. to 130 C., and the duration of said immersion being about from 0.5 hour to 10 hours,

(f) washing the thus-reacted textile to remove excess polyamine, and

(g) drying the washed textile.

10. The process of claim 9 wherein the water-miscible, cellulose-inert solvent is ethanol.

11. The process of claim 9 wherein the inert aprotio solvent is benzene.

12. The process of claim 9 wherein the aliphatic poly= amine is ethylenediamine.

13. The process of claim 9 wherein the aliphatic poly amine is diethylenetriamine.

14. The process of claim 9 wherein the straight-chain alcohol is l-butanol.

15. The fibrous, crosslinked (aminoalkyl)aminochloro= deoxycellulose, in the form of a textile, produced by the process of claim 1.

16. The product of claim 15 wherein the textile form is a yarn.

17. The product of claim 15 wherein the textile form is a fabric.

18. The fibrous, crosslinked (aminoethyl)aminochloro= deoxycellulose, in the form of a textile, produced by the process of claim 4.

19. The fibrous, crosslinked (4 aminobutyl)aminochlorodeoxycellulose, in the form of a textile, produced by the process of claim 5.

20. The fibrous, crosslinked (6 aminohexyl)amino-= chlorodeoxycellulose, in the form of a textile, produced by the process of claim 6.

21. The fibrous, crosslinked 2-(2-aminoethylamino) ethylaminochlorodeoxycellulose, in the form of a textile, produced by the process of claim 7.

22. The fibrous, crosslinked (aminoalkyl)aminochlorodeoxycellulose, in the form of a textile, produced by the process of claim 9.

23. The fibrous, crosslinked (aminoethyl)aminochloro= deoxycellulose, in the form of a textile, produced by the process of claim 12..

24. The fibrous, crosslinked 2-(2-aminoethylamino) ethylaminochlorodeoxycellulose, in the form of a textile, produced by the process of claim 13.

References Cited Chem. Abs., 59, 6604b (1963). Chem. Abs., 61, 2045d (1964).

GEORGE F. LESMES, Primary Examiner I. CANNON, Assistant Examiner U.S. Cl. X.R.

81 E, 1 VA, 1 P, 31, 116, 100, DIG 2; 260-212 

